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CN105315533A - Manufacturing method of polyolefin-based multilayer composite porous film - Google Patents

Manufacturing method of polyolefin-based multilayer composite porous film Download PDF

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Publication number
CN105315533A
CN105315533A CN201510449479.1A CN201510449479A CN105315533A CN 105315533 A CN105315533 A CN 105315533A CN 201510449479 A CN201510449479 A CN 201510449479A CN 105315533 A CN105315533 A CN 105315533A
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CN
China
Prior art keywords
film
polyolefin
composite porous
porous
multilayer composite
Prior art date
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Pending
Application number
CN201510449479.1A
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Chinese (zh)
Inventor
姜贵权
朱东辰
金容庆
金在雄
金亨珉
成贞文
禹映准
李章源
郑仁和
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SK Innovation Co Ltd
SK IE Technology Co Ltd
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SK Innovation Co Ltd
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Publication of CN105315533A publication Critical patent/CN105315533A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
    • B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0083—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/261—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/262—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B01D2323/081—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/44—Relaxation steps
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H01M50/406—Moulding; Embossing; Cutting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)
  • Cell Separators (AREA)

Abstract

Provided is a manufacturing method of a polyolefin-based multilayer composite porous film, including: a) forming a composition including a polyolefin resin and diluent to a sheet; b) stretching the sheet and extracting the diluent to manufacture a film; c) performing heat-treatment on the manufactured film; and d) coating one surface or both surfaces of the heat-treated film with a coating solution containing a heat resistant resin, wherein step c) and step d) are continuously performed.

Description

The manufacture method of polyolefin MULTILAYER COMPOSITE porous-film
Technical field
The present invention relates to a kind of manufacture method of polyolefin MULTILAYER COMPOSITE porous-film.Relate more specifically to a kind of manufacture method that can use the polyolefin MULTILAYER COMPOSITE porous-film that also can realize excellent intensity and transmitance as battery interval part.
Background technology
In the past, the fine porous film of polyolefine (microporousfilm) due to chemical stability and excellence mechanical properties and be widely used as various battery separatory membrane (batteryseparator), separation strainer or microfiltration separatory membrane (membrane) etc.Wherein secondary cell porous-film not only requires the stability of battery, also requires high-caliber quality simultaneously.Recently along with heavy body, the high trend exported of secondary cell, require increasing for the high strength of porous-film, high permeability, thermostability and the raising in order to the characteristic of the porous-film of the elctrical stability of secondary cell during discharge and recharge.
Lithium secondary battery in order to the stability in improving battery manufacturing process and using and require high mechanical strength and thermostability, require high permeability to improve capacity and output.Such as, if the thermostability of porous-film declines, then due to the rising of temperature in battery, sustain damage or be out of shape and cause the short circuit between generating electrodes, making battery overheated or increase the danger of presence of fire.And, along with the range of application of secondary cell is extended to hybrid vehicle etc., guarantee that the stability of the battery of overcharge is particularly important, and then requirement can resist the characteristic of the porous-film of the Voltage force that overcharge causes.
In order to the damage of the porous-film occurring in battery manufacturing process or occurred by the tree-shaped crystallization produced on electrode in battery charge and discharge process etc. can be prevented, and then prevent interelectrode short circuit, therefore need high strength.And, if porous film strength is weak in high temperature, then may there is the short circuit that film rupture causes.And then the heating that between generating electrodes, short circuit causes/on fire/blast etc.Described high strength represents perforation strength in the present invention.
In order to promote the capacity of lithium secondary battery and output and need high permeability.Along with the trend of the high capacity and high output that require lithium secondary battery, the requirement of the porous-film with high permeability is also being increased.
The thermostability of battery is subject to the closing temperature of porous-film , melt fracture temperature and percent thermal shrinkage etc. impact.Wherein, in high temperature, the impact of percent thermal shrinkage on the thermostability of battery is large.If percent thermal shrinkage is high, then, when inside battery forms high temperature, in contraction process, a part of electrode exposes, the short circuit between generating electrodes, causes heating/on fire/blast etc. thus.Even if the melt fracture temperature of porous-film is high, if percent thermal shrinkage is large, then in the process of porous-film intensification, a part of electrode exposes, the short circuit between generating electrodes.
The method of the contraction for reducing porous-film is disclosed in No. 1999-322989, Japanese Laid-Open Patent (patent documentation 1).This method is in order to reduce horizontal thermal contraction, and only to longitudinal stretching film or reduction total drawing ratio, because the physical property that can not obtain being obtained by drawing process promotes effect, its physical property is bad.And, because product perforation strength is at normal temperatures 0.06 ~ 0.11N/ μm of degree, very low, be therefore difficult to the stability promoting battery.
As mentioned above, existing porous-film has following problem, namely, the high strength needed for the stability in order to improve the secondary cell that heavy body/height exports and high permeability, low heat shrinkage can not be realized, in order to improve heat shrinkability characteristic, coating heat-resistant resin and/or inorganic particles and manufacture MULTILAYER COMPOSITE porous-film time, productivity declines greatly, and expense rises greatly.
Prior art document
Patent documentation
Patent documentation: No. 1999-322989th, Japanese Laid-Open Patent (1999.11.26)
Summary of the invention
The present invention proposed to solve the problem, and its object is to provide a kind of stability in order to promote lithium secondary battery and has high strength and high permeability, low-shrinkage, and the manufacture method of the polyolefin composite porous film of productivity excellence.
To achieve these goals, the invention provides a kind of this method of polyolefin MULTILAYER COMPOSITE porous-film, wherein, comprising: be a) step of sheet material by the composition molding comprising polyolefin resin and thinner,
B) stretch described sheet material and extract thinner to manufacture the step of film,
C) by the step that the film of described manufacture is heat-treated, and
D) step of the coating fluid of heat-resistant resin is contained in the one or both sides coating through described heat treated film,
Described c) step and d) step implement continuously.
The manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to an embodiment of the invention, wherein, c) thermal treatment of step comprises heat fixation, can also comprise film at least to a direction thermal stretch or hot wire-CVD operation.
The manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to an embodiment of the invention, wherein, hot wire-CVD operation can be shunk with the ratio of 50 ~ 99% of width before hot wire-CVD.
The manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to an embodiment of the invention, wherein, b) stretch ratio of step longitudinally and is laterally being respectively more than 4 times, and total drawing ratio is 20 ~ 80 times, c) step hot-draw ratio vertical or horizontal can be 1.01 times ~ 2.0 times.
The manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to an embodiment of the invention, wherein, a) composition of step can comprise polyolefin resin 15 ~ 50 % by weight and thinner 85 ~ 50 % by weight.
The manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to an embodiment of the invention, wherein, the weight-average molecular weight of polyolefin resin can be 1 × 10 5~ 2 × 10 6g/mol.
The manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to an embodiment of the invention, wherein, also comprises and e) film of the coating of described d) step is carried out dry step, and described drying can comprise and utilizes air or infrared-type drying installation.
The manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to an embodiment of the invention, wherein, the stretching process of described b) step is implemented temperature to the scope of the fusing point of polyolefin-based resins of lower than the fusing point of polyolefin-based resins 40 DEG C, and the heat treatment step of described d) step is implemented temperature to the scope of the temperature of higher than the fusing point of polyolefin-based resins 10 DEG C of lower than the fusing point of polyolefin-based resins 30 DEG C.
The manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to an embodiment of the invention, wherein, d) heat-resistant resin of step can comprise fusing point or second-order transition temperature is the water-soluble polymer of more than 150 DEG C or water-insoluble polymer.
The manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to an embodiment of the invention, wherein, water-soluble polymer can be selected from polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, carboxymethyl cellulose, Natvosol, maleic anhydride series resin, dextrin and composition thereof more than one
Water-insoluble polymer can be selected from Polyphenylene Sulfone one or more mixture in polysulfones, polyimide, polyamidoimide, polyarylamide, polyarylester, polycarbonate, poly(vinylidene fluoride) and multipolymer thereof.Or, can be comprise the acrylate-based water-insoluble polymer that second-order transition temperature is-60 DEG C ~ 0 DEG C.
Polyolefin MULTILAYER COMPOSITE porous-film according to the present invention realizes the advantage of low percent thermal shrinkage while having the physical strength and transmitance that can realize excellence.
And, manufacture method according to polyolefin MULTILAYER COMPOSITE porous-film of the present invention has the following advantages, be coated with continuously due under the state that can manufacture in the operation of batching without other, roll out or batching again the base material porous-film for the manufacture of porous-film, therefore, it is possible to the minimization of loss of the porous-film that may produce in operation, the porous-film occurred when base material porous-film can be batched is out of shape that the coating caused is bad to be minimized, thus lifting productivity, very economical.
Particularly, described base material porous-film has the ununiformity of thickness to a certain degree, when described base material porous-film is batched more than certain length, relatively thick part is along with the carrying out of coiling process, and the height of crimping portion is higher, makes the additional film batched produce distortion, and the base material porous-film of distortion is when rolling out to carry out being coated with, produce sagging or fold, cause bad in painting process, affect productivity.In addition, when the base material porous membrane cartridge batched is produced the composite porous film of coating on coating apparatus, produce through pin the loss of the porous-film of the length of drying installation etc., this being lost in each all can occur when exchanging the roller of base material porous-film.And each when exchanging new roller in the coiling process again of the batching of base material porous-film, composite porous film, certain length part above, due to fold etc., cannot batch qualified product, and then produces loss.The present invention is owing to can implement manufacture and the coating of base material porous-film continuously, and having can by the advantage of described minimization of loss.
Embodiment
Below the manufacture method of polyolefin MULTILAYER COMPOSITE porous-film of the present invention is described in detail.The embodiment introduced below is the example provided to fully transmit thought of the present invention to those skilled in the art.And the technical terms of use and scientific words, as without other definition, then represent the implication that those skilled in the art are known.
The present inventor finds, when manufacturing polyolefin MULTILAYER COMPOSITE porous-film, comprise thermal stretch, hot wire-CVD or heat fixation operation, low percent thermal shrinkage is realized while regulating the formation of the combination of described operation can realize excellent physical strength and transmitance, base material porous-film for the manufacture of porous-film is not needed other operations such as batching, roll out or batch, by the minimizing deformation of porous-film, the effect that can overcome the productivity decline that defective products causes can be realized, thus complete the present invention.
The invention provides a kind of manufacture method of polyolefin MULTILAYER COMPOSITE porous-film, it is characterized in that, comprise: a) utilize the composition comprising polyolefin resin and thinner that sheet material is carried out shaping step, b) stretch described sheet material and extract thinner to manufacture the step of film, c) by the step that the film of described manufacture is heat-treated, and the step of the coating fluid of heat-resistant resin d) is contained in the one or both sides coating through described heat treated film; In described c) step and d) in step, c) the described step of the heat treated film of step implements continuously.
Below each step of the present invention is described in detail.
Described a) step is the operation of sheet material by the composition molding comprising polyolefin resin and thinner.Described polyolefin-based resins can be the polyolefin-based resins of more than a kind separately or comprise the polyolefin-based resins of described more than a kind and the mixing element of inorganics or other resins except polyolefin-based resins.
Described polyolefin-based resins is restriction not, can comprise and be selected from ethene, propylene, alpha-olefin, 4-methyl-1-pentene etc. as the polyolefin-based resins of more than a kind in polyethylene, polypropylene and poly(4-methyl-1-pentene) etc. that monomer and comonomer use.That is, can be used alone described polyolefin-based resins, or use its multipolymer or mixture etc.
In the present invention, from the viewpoint of intensity, the heat-resistant quality etc. extruding mixing property, stretchiness and final porous-film, the preferred example of polyolefin-based resins can use co-monomer content to be less than high density polyethylene(HDPE) or its mixture of 2%.
The weight-average molecular weight of described polyolefin-based resins can be 1 × 10 5~ 2 × 10 6g/mol, is more preferably 2 × 10 5~ 1 × 10 6g/mol.Described weight-average molecular weight is less than 1 × 10 5during g/mol, porous film strength may decline, more than 2 × 10 6during g/mol, owing to extruding mixing behavior and stretchiness is poor, the outward appearance of porous-film and homogeneity are declined, is difficult to realize high permeability.
And, described resin combination is in order to promote thermotolerance and the through performance of porous-film, the added ingredients comprising inorganics or polyolefinic lifting thermotolerance and perviousness can be added further, as long as the resin of thermotolerance and perviousness can be promoted, be not limited to this.At this moment, the component content of described further interpolation accounts for less than 20 % by weight of composition, is preferably 0.1 ~ 20 % by weight, and this is conducive to the physical strength promoting porous-film.As an example of described inorganics, calcium carbonate, silicon-dioxide, barium sulfate, talcum or its mixture etc. can be enumerated, but be not limited to this.
The described resin that can promote thermotolerance and perviousness can enumerate as with the different types of resin of polyolefine be selected from polyamide resin (nylon system resin), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polychlorotrifluoroethylene (PCTFE), polyoxymethylene (POM), fluorinated ethylene propylene (PVF), polyvinylidene difluoride (PVDF) (PVdF) polycarbonate, polyarylester, polysulfones, polyetherimide and composition thereof more than one, but be not limited to this.
And described resin combination if needed, adds the general additive that oxidation stabilizer, UV stablizer, antistatic agent etc. can promote specific function further in the scope that can decline not significantly in the characteristic of porous-film.
In the present invention, described thinner can use the polyolefin-based resins that can use in extrusion temperature and resin combination to form the organic compound (organiccompound) of single-phase ad lib.As a preferred example, nonane (nonane) can be enumerated, decane (decane), naphthalane (decalin), paraffin oil (paraffinoil), aliphatics (aliphatic) or the cyclic hydrocarbon (cyclichydrocarbon) such as paraffin (paraffinwax), dibutyl phthalate (dibutylphthalate), the phthalic esters (phthalicacidester) such as dioctyl phthalate (DOP) (dioctylphthalate), palmitinic acid, stearic acid, oleic acid, linolic acid, the carbonatomss such as linolenic acid are the fatty acid of 10 ~ 20, palmityl alcohol, stearyl alcohol, the carbonatomss such as oleyl alcohol are aliphatic alcohols and their mixture etc. of 10 ~ 20.Wherein, the composition high as harmless, boiling point (boilingpoint), volatility (volatile) composition is few, preferably can use paraffin oil, the paraffin oil that the kinematic viscosity (kineticviscosity) being more preferably used in 40 DEG C is 20cSt ~ 200cSt.If the kinematic viscosity of described paraffin oil is more than 200cSt, then the kinematic viscosity owing to extruding in operation is too high, can produce the problems such as load rises, the surface of sheet material and film is bad, in abstraction process, owing to extracting difficulty, productivity can be produced and decline, the problems such as the transmitance minimizing that residual oil causes.If the kinematic viscosity of paraffin oil is less than 20cSt, then due in forcing machine with the differences in viscosity of molten polyethylene, make to extrude and add man-hour, mixing difficulty.
The ratio of mixture of polyolefin-based resins and thinner preferably uses with the weight ratio of 15 ~ 50:85 ~ 50 in melting/mixing/extrude in operation by the sheet composition comprising polyolefin resin and thinner in the present invention.When the ratio of polyolefin-based resins is less than 15 weight ratio, due to excessive low viscosity thinner, the not easily sheet material of uniform in shaping, due to sufficient orientation can not be formed in drawing process, not easily guarantee its physical strength, because the sheet material that produces is fragile, the problem such as may to break in drawing process.In addition, if more than 50 weight ratios, then owing to extruding the increase of load, its extrusion moulding declines, and along with the transmitance of porous-film declines greatly, sheet material is really up to the mark, stretching that may be uneven.
Described sheet composition uses that design double-shaft mixer, mixing roll or Banbury mixer etc. in order to the mixing of mixing polyolefin-based resins and thinner to carry out melting/mixing, obtains the mixture of single-phase.At this moment, extrusion temperature for the temperature (contrasting high more than 30 DEG C with resin melt temperature) that can make used resin and exist with single-phase with thinner with liquid state completely more applicable, be preferably 160 ~ 300 DEG C, be more preferably 180 ~ 250 DEG C.Its mixture extrudes cooling by T mould (T-die), is shaped to sheet form, by utilizing water-cooled or air-cooled casting (casting) or prolonging pressure (calendaring) method, the sheet material of shaping solid phase.Polyolefine and thinner input mixing machine can be mixed in advance, or drop into respectively from the feeder (feeder) be separated.
Then, implement as b) step described stretched sheet and extract the operation of thinner.
The axle difference of the sheet material roll-type manufactured in described operation or tentering type (tentertype) stretch or the method that simultaneously stretches with stretch ratio longitudinally and be transversely respectively more than 4 times, total drawing ratio is that 20 ~ 80 times of limit heating edge stretch.When the stretch ratio in a direction is less than 4 times, because the polyolefinic orientation in porous-film is insufficient, high strength cannot be guaranteed.And when total drawing ratio is less than 20 times, not only produces and do not stretch, its physical property is also bad, if more than 80 times, then in stretching, produce the possibility of breaking high, also have the shortcoming that the shrinking percentage of most telolemma increases.The temperature implementing to stretch is that [fusing point of polyolefin-based resins-40 DEG C] ~ [fusing point of polyolefin-based resins] is more applicable.When polyolefin-based resins be not a kind of but mixture time, using the fusing point of the highest resin of content as the fusing point of polyolefin-based resins.
Temperature is less than [fusing point of polyolefin-based resins-40 DEG C], then due to the condition of the mobility of polyolefin-based resins inner macromolecule chain can not be guaranteed, stretching uneven in drawing process and breaking, drawing stability cannot be guaranteed, the transmitance of final porous-film is too low, cannot manufacture the porous-film of high-quality.And, temperature is greater than [fusing point of polyolefin-based resins], then due to overheated, sufficient tension force cannot be applied to film, the excessive tensile of generating portion, cannot guarantee the homogeneity of quality, owing to fully cannot form the orientation of resin in sheet material, final porous film strength is reduced, high security battery porous-film cannot be manufactured.Usual polyvinyl resin is preferably implemented to stretch 100 DEG C ~ 140 DEG C scopes.
After the film that above-mentioned steps stretches is utilized the thinner of organic solvent extraction inside, carry out drying.There is no particular limitation for the organic solvent that can use in the present invention, as long as any solvent that can extract the thinner of resin extruded middle use can use, but can preferably use extraction efficiency high and the methylethylketone of fast drying, methylene dichloride, normal hexane etc.
All solvent extraction process that extracting method can be distinguished or compound use dipping (immersion) method, solvent spray (solventspray) method, ultrasonic wave (ultrasonic) method etc. are general.And the content of residual diluent will below 2 % by weight during extraction.The content of residual diluent is more than 2 % by weight, then physical property declines, and the transmitance of film reduces.The amount (extraction yield) of residual thinner receives the impact of Extracting temperature and extraction time greatly.With regard to Extracting temperature, although the solubleness in order to increase thinner and solvent, preferable temperature is more high better, and consider the safety problem that solvent boiling (boiling) causes, Extracting temperature is preferably below 40 DEG C.Extraction time is different along with the thickness of the film produced, and when producing the general fine porous film of 10 ~ 30 μm of thickness, 2 ~ 4 minutes more suitable.Replace the film of thinner by drying process through leaching process with organic solvent, final dry organic solvent, manufactures fine porous film.Tension adjustment shrinkage character and physical property can be applied in this extraction/drying process.
Implement afterwards c) as the heat treatment step of the step that the film manufactured after above-mentioned b) step is heat-treated.
The residual stress of the film that removing is dry, and then implement to reduce the shrinking percentage of most telolemma and change the heat treatment step of air hole structure.Heat treatment step can be divided into the steps such as thermal stretch, heat fixation, hot wire-CVD.Thermal stretch step is with by utilizing the device of roller or tentering (tenter) mode and under carrying out heating condition, the step stretched is implemented respectively or simultaneously to longitudinal direction (MD) and horizontal (TD), be expand the operation of pore by making porous-film internal interface open, its multiplying power longitudinally, is laterally being preferably 1.01 times ~ 2.0 times respectively.Stretching ratio is more than 2.0 times, then due to excessive tensile, porous-film may break in drawing process, produces the pore opening of porous-film and the excessive problem of shrinking percentage.Heat fixation step is the device utilizing roller or tentering mode, with do not occur in length and width numerical value change mode force hold state under, add the step of residual stress in heat extraction film.Hot wire-CVD step is the device utilizing roller or tentering mode, under heating condition, at longitudinal direction (MD) and 99% ~ 50% ([after hot wire-CVD step length/width] ÷ [before hot wire-CVD step length/width]) of length/width before laterally the size of length and width respectively or is simultaneously reduced to hot wire-CVD step by (TD), and then reduce the step of residual stress and shrinking percentage.In order to fully reduce shrinking percentage, implementing to shrink (relaxing) to less than 99%, shrinking (relaxing) if implement and be less than 50%, although then can low-shrinkage be obtained, transmitance can be made too low.Heat treatment step can optionally or compound repeat implement thermal stretch, heat fixation, hot wire-CVD step.Heat treatment step needs to implement between [polyolefin-based resins fusing point-30 DEG C] to [polyolefin-based resins fusing point+10 DEG C].Polyolefin-based resins be not a kind of but mixture time, using the fusing point of the highest resin of content as the fusing point of polyolefin-based resins.Operation is heat-treated in the temperature being less than [polyolefin-based resins fusing point-30 DEG C], then carry out thermal stretch, heat fixation, hot wire-CVD along with under the state of mobility not guaranteeing chain in resin, fully can not remove internal stress of resin, shrinking percentage becomes large, in thermal stretch step, produce the problems such as film rupture, produce the problem that pore is excessive.Operation is heat-treated in the temperature being greater than [polyolefin-based resins fusing point+10 DEG C], although then due to the abundant mobility of chain in resin can be kept, fully carry out stress mitigation, shrinking percentage is had to decline a little, but due to air hole structure collapse, too low transmitance can only be realized, the porous-film of high permeability cannot be manufactured.Usually, 110 DEG C ~ 140 DEG C are adopted during highdensity polyethylene.And the time of heat treatment step can be relatively short when temperature height, relatively long when temperature is low.Be preferably 10 seconds ~ about 2 minutes.
Then, implement d) in the operation of the coating fluid of one or both sides coating containing heat-resistant resin of described heat treated film.
In order to improve thermotolerance, being mixed with the solution of polymer and/or inorganics in the one or both sides coating of the base material of the porous-film of above-mentioned steps manufacture, under suitable humidity and temperature and air quantity, implementing the step except desolventizing and drying.At this moment the heat-resistant resin be suitable for can be divided into water-soluble polymer and water-insoluble polymer according to the solubleness of water, water-soluble polymer resin has melt temperature (Tm) or second-order transition temperature (Tg) or the polyvinyl alcohol of carbonization temperature more than 150 DEG C, polyacrylamide, polyvinylpyrrolidone, Walocel MT 20.000PV, Natvosol, dextrin etc., but is not limited to this.Above-mentioned water-insoluble macromolecule resin can be one or more the mixture polymer be selected from melt temperature (Tm) Polyphenylene Sulfone more than 150 DEG C, polysulfones, polyimide, polyamidoimide, polyarylamide, polyarylester, polycarbonate, poly(vinylidene fluoride) and multipolymer thereof, but is not limited to this.At this moment, when described high molecular heat resisting temperature is below 150 DEG C, due to close to the melt temperature as the polyethylene porous membrane of base material, in the high temperature of 130 ~ 160 DEG C, possibly heat shrinkability characteristic cannot be improved.
And in order to give Heat-resistant adhesive power further, described water-insoluble polymer can also optionally containing comprising the acrylate-based emulsion form latex particle that second-order transition temperature (Tg) is-60 DEG C ~ 0 DEG C.At this moment, if Tg is below-60 DEG C, then due to low Tg, under latex state, gelatin phenomenon is serious, may produce coacervation, if Tg is more than 0 DEG C during coating solution with inorganic particulate, then because bounding force between inorganic particulate or the bounding force between inorganic particulate and base material decline, the phenomenon that the inorganic particulate that coating layer occurs departs from.
The solvent used in described coating solution not by considerable restraint, but preferably uses and can dissolve heat-resistant resin and can the solvent of dispersed inorganic particle.The example of described solvent comprises tetrachloroethane (tetrachloroethane), methylene dichloride (methylenechloride), chloroform (chloroform), 1,1,2-trichloroethane (1,1,2-trichloroehtane), tetrahydrofuran (THF) (tetrahydrofuran), two alkane (1,4-dioxane), chlorobenzene (chlorobenzene), pimelinketone (cyclohexanone), dimethyl formamide (dimethylformamide), acetone (acetone), dimethyl sulfoxide (DMSO) (dimethylsulfoxide), N-Methyl pyrrolidone (n-methtl-2-pyrrolidone), N,N-DIMETHYLACETAMIDE (dimethylacetamide), water (water), ethanol (alcohol) etc. more than one, but described example can not limit scope of the present invention.
In order to give high permeability and stability, the inorganic particulate used in the present invention preferably uses median size to be the inorganic particulate of 0.3 ~ 2 μm.If median size is less than 0.3 μm, then the operation of dispersed particle needs for a long time, and the voidage of coating layer declines, and the specific surface area of particle becomes large.To this, using a large amount of heat-resistant resins to give bounding force, causing the consequence that the transmitance of whole porous-film declines.And, if when median size is more than 2 μm, due to the filming difficulty of coating layer, does not form inorganic particulate and fill fully, in lifting heat-resistant quality, have limitation.
As the example of described inorganic particulate, calcium carbonate, aluminum oxide, aluminium hydroxide, silicon-dioxide, barium titanium oxide, magnesium oxide, magnesium hydroxide, talcum, clay, titanium oxide etc. can be used alone or as a mixture, but be not limited to this.
Although in the present invention without particular limitation of, but described heat-resistant resin and inorganic particulate manufacture with 20/80 ~ 2/98 (% by weight) and form, if the ratio of heat-resistant resin and inorganic particulate is less than 20/80, then not easily realize sufficient transmitance, if more than 2/98, then bounding force significantly declines.Coating layer is preferably 1 ~ 6 μm, if be less than 1 μm, then not easily passs through the applicable lifting thermotolerance of inorganic particulate, and inorganic particulate fully cannot play and uses acting on the isolation (spacer) of electrode of causing of inorganic particulate.If on the contrary more than 6 μm, then because coating thickness is high, the bounding force of coating layer declines, and transmitance significantly reduces, and cannot design and be applicable to the high battery exporting heavy body.
The method of the solution that coating heat-resistant resin and inorganic particulate form can use normally used method.As an example, comprise rod (bar) coating method, roller (rod) coating method, mould (die) coating method, line (wire) coating method, comma (comma) coating method, micro gravure coating/intaglio plate coating (microgravure/gravure) method, dipping (dip) coating method, spraying (spray) method, rotation (spin) coating method or these hybrid mode and mode of texturing etc. and use.The process of the coating using scraper plate (doctorblade) or air knife (airknife) removing part surface can also be comprised afterwards.
Can further include the step of the film be coated with in e) dry described d) step.
Coating on base material is coated at certain temperature and humidity, by drying process, through removing the step of the solvent used together with solution state.At this moment, drying means is not particularly limited, and air or the device such as infrared-type drying installation and ultrasonic drying device can be utilized to implement.
As mentioned above, according to the manufacture method of polyolefin MULTILAYER COMPOSITE porous-film of the present invention, in order to ensure the productivity of excellence, operation needs sheet material and film constantly, with continuous print operation to carry out.Especially c) behavioural characteristic is entered continuously to d) step with above-mentioned.By carrying out like this, thus there is no other the operation of batching, rolling out and batching again, carrying out continuously, excellent productivity can be guaranteed.
Below, by following examples, the present invention is described in more detail, but scope of the present invention is not limited to this.
(evaluation)
1. molecular weight
The molecular weight of polyolefin-based resins utilizes the high temperature GPC (GelPermeationChromatography) of PolymerLaboratory company, with 1,2,4-trichlorobenzene (1,2,4-trichlorobenzene) (TCB) is solvent, measures at 140 DEG C, and the standard model of molecular weight determination employs polystyrene (Polystyrene).
2. Thermal characteristic analysis
DSC (differential scanning calorimeter (DifferentialScanningCalorimetry), MettlerToledo company DSC-822E) is utilized to analyze the fusing point (Tm) of polyolefin-based resins.The analysis condition of polyolefin-based resins and heat-resistant resin is as follows, get 5mg sample, be warming up to resin with sweep velocity (scanningrate) 10 DEG C/min to melt completely, 10 minutes are maintained in this temperature, after arriving complete molten state, be cooled to 0 DEG C with sweep velocity (scanningrate) 10 DEG C/min, make its crystallization turn to complete solid state, then determine the fusing point of resin with sweep velocity (scanningrate) 10 DEG C/min intensification.
3. film thickness
Utilize the TESAMu-HiteElectronicHeightGauge of TESA company, it is 0.63N that setting measures pressure, determines the thickness of the finished product.
4. perforation strength
Install that diameter is 1mm, radius-of-curvature is the pin of 0.5mm the UTM (universal testing machine (universaltestingmachine)) of Instron company is upper, at 23 DEG C, determine with the translational speed of 120mm/min break porous-film time porous film strength.Illustrate with N/ μm with thickness normalized value.
5. gas permeation rate
Gas permeation rate is determined with PORE SIZE APPARATUS FOR (CFP-1500-AEL of porometer:PMI company).Usual gas permeation rate represents with lattice profit number (Gurleynumber), but does not revise the impact of porous-film thickness due to the sharp number (Gurleynumber) of lattice, is difficult to the relative permeability of the gap structure obtained according to porous-film self.In order to address this problem, be employed herein darcy (Darcy's) transmitance constant.Darcy (Darcy's) transmitance constant can obtain from mathematical expression below, is employed herein nitrogen.
C＝(8FTV)/(πD 2(P 2-1))
C here: darcy transmitance constant
F: flow velocity
T: thickness of sample
V: gas viscosity (0.185forN2)
D: sample diameter
P: pressure
In the present invention, in 100 ~ 200psi region, employ the mean value of darcy (Darcy's) transmitance constant.
6. shrinking percentage
After composite porous film is cut into 10cm × 10cm, put between Teflon film, put into size and be 11cm × 11cm and thickness is between the sheet glass of 3mm, put into the baking oven (JEIOTECH company OF-12GW) that temperature-stable is 150 DEG C, place after 60 minutes, measure its size variation, calculate its shrinking percentage.The calculating formula of shrinking percentage is as shown in the formula 1.
[formula 1] shrinking percentage (%)=100 × (100mm – is placed on the length after 150 DEG C)/100mm
7. productivity
When employing continuous seepage more than 20 hours, the turnout (m of base material porous-film salable product after unit time (1hr) interior heat treatment step 2/ hr) terminate with heat treatment step after porous-film through being coated with the turnout (m of the composite porous film salable product manufactured 2/ hr) ratio.Formula 2 below the calculating use of productivity.In order to compare under same benchmark, the turnout of unit time turnout as base material porous-film of the film (before being coated with base material porous-film) of heat treatment step will be carried out in manufacturing method according to the invention and discontinuous manufacture method.More specifically, although loss, the loss etc. that produces in discontinuous operation that the roller batched alternately produces are included in the turnout of base material porous-film, get rid of outside composite porous film turnout.
[formula 2] productivity (%)=(composite porous film turnout (m 2/ hr))/(base material porous-film turnout (m 2/ hr)) × 100
[embodiment 1]
Be 3.0 × 10 by weight-average molecular weight 5, fusing point is that the high density polyethylene(HDPE) of 135 DEG C uses as polyolefin-based resins, the paraffin oil being 160cSt 40 DEG C of kinematic viscosity is used as thinner.The ratio of components of polyolefin-based resins and thinner is 28 % by weight and 72 % by weight.
Utilize double-shaft mixer to extrude described composition at 230 DEG C, utilize T mould (T-die) and casting roll to manufacture sheet material.By this sheet material with 112 DEG C of longitudinal directions 7.5 times, 126 DEG C of transverse directions 6 doubly carried out axle difference stretch.The film stretched utilizes the methylene dichloride of 25 ~ 30 DEG C to be extracted thinner under the state applying tension force.Heat treatment step is longitudinally implemented at 129 DEG C, and each step is carried out with the order of thermal stretch to 1.5 times, heat fixation, hot wire-CVD to 80%, and the width of the base material porous-film at this moment manufactured is 1000mm.
Coating is implemented continuously to the base material porous-film manufactured in this way.
The coating fluid that coating uses is by Al 2o 3powder (median size 0.5 μm) 45 % by weight and melt temperature to be polyvinyl alcohol 2.0 % by weight, the second-order transition temperature of 220 DEG C be acrylic latex (Acryliclatex) solids component 1.5 % by weight of-45 DEG C and deionized water 51.5 % by weight form, and manufactured solution in advance and use before coating.
Coating be to the base material porous-film manufactured in this way with continuous print operation, with coating width 900mm after coated on one side coating fluid, being set as the interval inner drying/except desolventizing of 110 DEG C, finally producing and there is the polyolefin composite fine porous-film that thickness is the coating layer of 5.0um.Cut out the two ends removing not have part and the film be coated with, the width of final composite porous film is 800mm, and its production rate is 5m/min, and the product produced has replaced roller in units of 500m.The product loss producing 20m in the process of the roller be wound around is replaced with new roller.Physical property and the productivity of the composite porous film manufactured represent in the following Table 1.
[embodiment 2]
Be 3.8 × 10 by weight-average molecular weight 5, fusing point is that the high density polyethylene(HDPE) of 135 DEG C uses as polyolefin-based resins, the paraffin oil being 160cSt 40 DEG C of kinematic viscosity is used as thinner.The ratio of components of polyolefin-based resins and thinner is 33wt% and 67wt%.
Utilize double-shaft mixer to extrude described composition at 230 DEG C, utilize T mould (T-die) and casting roll to manufacture sheet material.By this sheet material with 115 DEG C of longitudinal directions 6.5 times, 127 DEG C of transverse directions 6.5 doubly carried out axle difference stretch.The film stretched utilizes the methylene dichloride of 25 ~ 30 DEG C to be extracted thinner under the state applying tension force.Heat treatment step is longitudinally implemented at 131 DEG C, and each step is carried out with the order of thermal stretch to 1.6 times, heat fixation, hot wire-CVD to 78%, and the width of the base material porous-film at this moment manufactured is 1000mm.Continuous coating has been carried out to the base material porous-film manufactured in this way.
The coating fluid that coating uses is by Al 2o 3to be polyvinyl alcohol 1.9wt%, the second-order transition temperature of 220 DEG C be that acrylic latex (Acryliclatex) the solids component 1.4wt% of-45 DEG C and deionized water 50.7wt% forms for powder (median size 0.8 μm) 46wt% and melt temperature, manufactured solution in advance and use before coating.
Coating be to the base material porous-film manufactured in this way with continuous print operation, with coating width 900mm after coated on one side coating fluid, being set as the interval inner drying/except desolventizing of 110 DEG C, finally producing and there is the polyolefin composite fine porous-film that thickness is the coating layer of 5.0um.Cut out the two ends removing not have part and the film be coated with, the width of final composite porous film is 800mm, and its production rate is 5m/min, and the product produced has replaced roller in units of 500m.The product loss producing 20m in the process of the roller be wound around is replaced with new roller.Physical property and the productivity of the composite porous film manufactured represent in the following Table 1.
[comparative example 1]
Utilizing single axle extruding machine at 200 DEG C, extrude weight-average molecular weight is 1.5 × 10 5, fusing point is the high density polyethylene(HDPE) of 134 DEG C, utilizes T mould (T-die) and casting roll to manufacture film.This film is utilized the drawing machine of roll shape, after cold stretching to 1.5 at normal temperatures times, 110 DEG C of thermal stretchs to 2.2 times, carry out heat fixation at 120 DEG C, manufacture base material porous-film with drying process.The width of the porous-film at this moment manufactured is 500mm, and its production rate is 5m/min, has replaced roller, make its product length reach 500m after implementing coating in units of 530m.The product loss producing 20m in the process of the roller be wound around is replaced with new roller.The base material porous-film manufactured in this way is delivered to coating apparatus, and utilization rolls out while machine rolls out and is coated with.
The coating fluid that coating uses is by Al 2o 3to be polyvinyl alcohol 2.1wt%, the second-order transition temperature of 220 DEG C be that acrylic latex (Acryliclatex) the solids component 1.3wt% of-45 DEG C and deionized water 52.1wt% forms for powder (median size 0.5 μm) 44.5wt% and melt temperature, manufactured solution in advance and use before coating.
Coating be to the base material porous-film manufactured in this way with continuous print operation, with coating width 450mm after coated on one side coating fluid, being set as the interval inner drying/except desolventizing of 110 DEG C, finally producing and there is the polyolefin composite fine porous-film that thickness is the coating layer of 5.0um.Cut out the two ends removing not have part and the film be coated with, the width of final composite porous film is 400mm, and its production rate is 5m/min, and the finished product length is 500m.Produce 20 hours altogether, confirm that the result of the coating disqualification rate that the sagging or fold of the base material porous-film owing to rolling out causes is 18%.For the product of 500m length, at a local generation unacceptable product, then the whole length comprising the place producing unacceptable product can not be used.Physical property and the productivity of the composite porous film manufactured represent in the following Table 1.
[comparative example 2]
Be 3.0 × 10 by weight-average molecular weight 5, fusing point be the high density polyethylene(HDPE) of 135 DEG C as polyolefin-based resins, will be that the paraffin oil of 160cSt is as thinner 40 DEG C of kinematic viscosity.The ratio of components of polyolefin-based resins and thinner is 30wt% and 70wt%.
Utilize double-shaft mixer to extrude described composition at 230 DEG C, utilize T mould (T-die) and casting roll to manufacture sheet material.By this sheet material with 116 DEG C of longitudinal directions 6 times, 124 DEG C of transverse directions 5.5 doubly carried out axle difference stretch.The film stretched utilizes the methylene dichloride of 25 ~ 30 DEG C to be extracted thinner under the state applying tension force.Heat treatment step is longitudinally implemented at 130 DEG C, and each step is carried out with the order of thermal stretch to 1.3 times, heat fixation, hot wire-CVD to 85%, and the width of the base material porous-film at this moment manufactured is 1000mm.Its production rate is 5m/min, has replaced roller, make its product length reach 500m after implementing coating in units of 530m.The product loss producing 20m in the process of the roller be wound around is replaced with new roller.The base material porous-film manufactured in this way is delivered to coating apparatus, and utilization rolls out while machine rolls out and is coated with.
The coating fluid that coating uses is by Al 2o 3to be polyvinyl alcohol 1.8wt%, the second-order transition temperature of 220 DEG C be that acrylic latex (Acryliclatex) the solids component 1.7wt% of-45 DEG C and deionized water 49.5wt% forms for powder (median size 0.5 μm) 47wt% and melt temperature, manufactured solution in advance and use before coating.
Coating be to the base material porous-film manufactured in this way with continuous print operation, with coating width 900mm after coated on one side coating fluid, being set as the interval inner drying/except desolventizing of 110 DEG C, finally producing and there is the polyolefin composite fine porous-film that thickness is the coating layer of 5.0um.Cut out the two ends removing not have part and the film be coated with, the width of final composite porous film is 800mm, and its production rate is 5m/min, and the finished product length is 500m.Produce 20 hours altogether, confirm that the result of the coating disqualification rate that the sagging or fold of the base material porous-film owing to rolling out causes is 12%.For the product of 500m length, at a local generation unacceptable product, then the whole length comprising the place producing unacceptable product can not be used.Physical property and the productivity of the composite porous film manufactured represent in the following Table 1.
[table 1]
As mentioned above, although the present invention is illustrated by limited embodiment, but this just provides more comprehensively understanding of the present invention to contribute to, the present invention is not limited to above-described embodiment, and person skilled in the art of the present invention can carry out various correction and distortion to these base materials.
Therefore, thought of the present invention is not limited to the embodiment illustrated, is not only claims, and all should regarding as that be impartial with claims or equivalent variations belongs to thought category of the present invention.

Claims (10)

1. a manufacture method for polyolefin MULTILAYER COMPOSITE porous-film, wherein, comprising:
A) be the step of sheet material by the composition molding comprising polyolefin resin and thinner;
B) stretch described sheet material and extract thinner to manufacture the step of film;
C) by step that the film of described manufacture is heat-treated; And
D) step of the coating fluid of heat-resistant resin is contained in the one or both sides coating through described heat treated film;
Described c) step and d) step implement continuously.
2. the manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to claim 1, wherein, the thermal treatment of described c) step comprises heat fixation, also comprises film at least to the operation of a direction thermal stretch or hot wire-CVD.
3. the manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to claim 2, wherein, described hot wire-CVD operation is shunk with the ratio of 50 ~ 99% of width before hot wire-CVD.
4. the manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to claim 2, wherein, the stretch ratio of described b) step longitudinally and is laterally being respectively more than 4 times, and total drawing ratio is 20 ~ 80 times,
C) step stretch ratio vertical or horizontal be 1.01 times ~ 2.0 times.
5. the manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to claim 1, wherein, the composition of described a) step comprises polyolefin resin 15 ~ 50 % by weight and thinner 85 ~ 50 % by weight.
6. the manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to claim 1, wherein, the weight-average molecular weight of the polyolefin resin of described a) step is 1 × 10 5~ 2 × 10 6g/mol.
7. the manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to claim 1, wherein, also comprises and e) film of the coating of described d) step is carried out dry step, and described drying comprises and utilizes air or infrared-type drying installation.
8. the manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to claim 3, wherein, the stretching process of described b) step is implemented temperature to the scope of the fusing point of polyolefin-based resins of lower than the fusing point of polyolefin-based resins 40 DEG C,
The heat treatment step of described d) step is implemented temperature to the scope of the temperature of higher than the fusing point of polyolefin-based resins 10 DEG C of lower than the fusing point of polyolefin-based resins 30 DEG C.
9. the manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to claim 1, wherein, the heat-resistant resin of described d) step comprises water-soluble polymer more than 150 DEG C of fusing point or second-order transition temperature or water-insoluble polymer.
10. the manufacture method of polyolefin MULTILAYER COMPOSITE porous-film according to claim 9, wherein, described water-soluble polymer be selected from polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, carboxymethyl cellulose, Natvosol, maleic anhydride series resin, dextrin and composition thereof more than one
Described water-insoluble polymer is one or more the mixture be selected from Polyphenylene Sulfone, polysulfones, polyimide, polyamidoimide, polyarylamide, polyarylester, polycarbonate, poly(vinylidene fluoride) and multipolymer thereof, or to comprise second-order transition temperature be-60 DEG C ~ 0 DEG C acrylate-based.
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